Halogenated indigoid dyestuffs



HERMANN STAUDINGER, OF ZURICH, RICHARD TOBLER AND ROBERT STOCK ER, OF BASEL, JAKOB Mfi'LLER, OF MUNGHENSTEIN, NEAR BASEL, AND ARM IN BUCHER, .OF EASIER-SWITZERLAND, ASSIGNORS TO THE FIRM SOCIETY OF CHEMICAL IN- DUSTRY IN BASIiE. OF BASED. SWITZERLAND.

HALOGENATED INDIGOID DYESTUFFS.

No Drawing. Original application filed Novembertl, 1923, Serial No. 876,858; and in Switzerland Decemher 7, 1922. Divided and'this application filed october 28, 1925. Serial No. 65,484.

The instant application, which is a'division of our application Serial No. 676,858, filed November 24, 1923, relates to new halogenated indigoid dyestufisj The invention comprises the new dyestufl's, as well as the material dyed with these dyestufis.

It has been found that indigoid dyestutfs are obtained by reacting with compounds of the general formula:

a OFX wherein C and G denote two carbon atomsof a naphthalene nucleus in ortho-position to each other, C being a B-carbonatom, and wherein C denotes a carbon atom to which there are attached exchangeable radicals a2, such as 0, two halides, one anil, H on reactive compounds of the general forwherein Ly denotes an exchangeable group, such as 0, two halides, one anil, H and All of these new dyestuifs are character 60 ized by the symmetrical grouping the first member of which is attached by the carbon atom C to the sulfur atom of-e these compounds.

wherein m, n,'and 1* denote atoms or residues of which two are carbon atoms adjacent to each other which at the same time belong to a ring of the naphthalene series, and of which the third atom maybe a C or a S atom.

i As compounds of the general formula:

there may be-mentioned the 1: 2- and 2:3-

thionaphthisatins, the 1:2- and 2:3-naphththioindoxyls, theirhalides and'anils, as well as the halogen substitution products of As compoundsof the general formulaz there may be mentioned the ,thionaphthisatins, naphththioindoxyls, acenapht-henequinones and acenaphthenones.

The reactions which take place are illustrated by the following equations:

bored condensed cyclic complex.

The dyeetufis thus obtained may be further. halogenated. v

1 ,i 5nd,;P1'DP9I-tl-N of some of the dyestuffs obtained according to the present invention are given in the table hereinafter.

Example.

396 parts of the dyestufi thus obtained are introduced into a solution containing 352 parts of bromine in 8000 parts of nitrobenzene. The reaction mixture is kept for some hours at ordinary temperature and then heated slowly, while stirring, to 140-150 C. in an oil bath, until. the bromine has disappeared. After cooling the dyestuff is filtered, washed with alcohol, and dried. It forms in a dry state a greenish-blue powder, dissolving in concentrated sulfuric acid with green coloratiomyielding an orangebrown vat from. which cotton is dyed pure and very fast blue tints.

The formula of the new dyestutl corresponds most probably with the formula of dyestufli' No. XV of the table.

i Colorincon- No. Coupling component I. Coupling component II. g fgg Oelfllggid Color of vat. G g ffS I 4-chl0rQ-1:2-thi0naphtl1isatin lz'z-naphththioindoxyl Greenblack... Violet Green-yellow. Gray. 11 p-dimethylamlno-anil of 2:3- Acenaplithenono and mono- Red Green Brown-orange Red.

thionaphthisatin. bromiuatlon. IIE idem r 2:3-naphththio1ndoxyl and Green1shblue. Green Orange Blue. mono-bromination. IV idem 2:3-naphththioindoxyl and id .id ..id Pure blue.

di-bromination. V l-chloro-Z:3-thionaphthisatin. cenaphthenone. Brown-yellow. Heliotrope. VI p'-dimethylamino-1-ehloro-2:3- idem .id [(1.

thionaphthisatin-anil. VII 1-bromo-2:3-thionaphthisatim. 1:2-naphththioindoxyl; Brown-black, Reddish-yel- Reddish vio- I ow. et. VIII .idem 2:3-naphththioindpxyl Blue-green... Orange Greenish-blue.

IX idem 2:3-naphtl 1th1oindoxyland ..id id Pure blue bromination. X 1:2-naphti1thioindoxyl Atenaphthzenequmone and Dark brown-. Green. Orange-brown. Brown.

romina 1013. XI #ohloro-l:2-naphththioindoxyl 4-chl0ro-l:3-thionuphthisatin. Gray-blue..-" Violet-red Yellow Blue. XII idem Acenaphthene-quinone Red Green Yellow Red-brownj XEII 1-chloro-2:3-naphththioindoxyl em t. Blu1sh-red Green Brown-orange. Bluish-red, XIV 8-cl1loro-2:3-naphththioindoxyl idem Deep red Deep green. Orange-brown. Bluish-red.

XV l-bromo-2Iii-naphththioindoxyl 1-bromo-2:3-thionaphth1sat1n Violet Ohye-green Olive-brown Blue.

5 The formula of the dyestufi No. VH is: The formula of dyestufi', No. XV is the following:

S Br I Bl fix J .0 0 l l l t g 0 \C What we claim is: 5 The formula of dyestufi No. X 1s the following eo=..,o 50 L i t t Theformula. of dyestufl No. XII is the 55 following: 1

1'. As new products the halogenated indigoid dyestufis which are characterized by the setrical atom grouping:

fi t t t the first member of which is attached by the carbon atom C5 to the sulfur atom of a t i-- oleus, which products torm'dark red to blue and greenish-black powders, dissolving in sulfuric acid of 98 per cent stren th with:

solution greenish-yellow to brownish-orange vats which dye cotton-brown to bluish-red and greenish-blue tints which are fast.

2. As new products the halogenated indigoid dyestuffs corresponding with the general formula:

corresponding with the general formula:

wherein both naphthalene nuclei are halogenated, which products form violet and green-blue powders, dissolving in sulfuric roducts the halogenated inclaim 4.

green eolorations, yielding with hydrosulfite and caustic soda solution orange to brownorange and olive-brown vats which dye cotton fast blue tints.

4. As new roducts thehalogenated indigoid dyestu s corresponding with the general formula:

halogen halogen t 0 o o 8 ll which products form violet and green-blue powders, dissolving in sulfuric acid of 98 per cent strength with brown to green colorations, yielding with hydrosulfite and caustic soda solution orange to brown-orange'and olive-brown vatswhich dye-cotton fast blue tints.

.5. Material claim-1. 6. Material claim 2.

7. Material dyed with the dyestuffs of claim 3.

8. Material dyed -with the dyestufis of dyed with the dyestuffs of dyed with the dyestufi's of In witness whereof we have hereunto signed our names this 2nd day of October 1925..

HERMANN STAUDINGER. RICHARD TOBLER. ROBERT STOCKER. JAKOB MULLER.

ARMIN BUCHER.

acid of 98 per cent strength with brown to 

